Ethers and their sulphonated derivatives



Patented May 13, 1941 UNITED STATES PATENT OFF-ice 2,241,421'

n'rncas AND 'rmam srmrnomrsn nsmvs'rrvns Donald Price and Bernard A. Dombrow, New York, N. Y., minors to National Oil Products Company, Harrison, N. J., a corporation of New Jersey I No Drawing. Application September 30, 1939,

. Serial No. 297,325

25 Olaims. (Cl- 260-513) This invention relates to the production of new ethers and their sulphonated derivatives, more particularly to the preparation of sulphonated ethers having wetting and detergent prop- I ethers and their sulphonated derivatives.

. It is a further object of this invention to prepare' substances having wetting and detergent properties and which are highly stable in alkaline solutions.

In accordance with our invention ethers are prepared having the general formula R I R! sweatenema.

in which R1 and R2 denote either hydrogen or alkyl radicals containing not more than 4 carbon atoms; Ra denotes an alkyl radical containing not more than 6 carbon atoms; R4 denotes a fatty alcohol radical containing from 6 to. 22 carbon atoms, preferably from 8 to 14 carbon atoms,'

and n is a whole number from 1 to 3. These ethers may, in accordance with our. invention, be suiphonated to produce highly surface active agents. For example, the preferred ethers, i. e. those in which R4 denotes a fatty alcohol radical containing from 8 to-14 carbon atoms, may be sulphonated so as to yield substances having The ethers of our invention may be prepared in any suitable manner known to the art. However, we prefer to prepare these ethers by reacting suitable derivatives of general formula Rx Rx nrc=toni).o'n in which R1, R2, R3 and n are as above defined, with a fatty alcohol containing from 6 to 22 carbon atoms. The short chain alcohol preferably einployed as a starting material in accordance with our invention is methallyl alcohol, since this alcohol is readily available and yields ethers which upon suiphonation gives products having excellent wetting or detergent properties. However,-it is to be understood that other alcohols having the above general formula may also be employed; such as, for example, ethallyl alcohol, 2-methyl crotyl alcohol, 3-methyl -3-butene l-ol and 4-methyl -4-pentene 1-ol.

" The fatty alcohol employed as starting material in accordance with our invention may be any of the fatty alcohols containing from 6 to 22 carbon atoms. The particular fatty alcohol employed ordinarily depends upon the nature of the ether or sulphonated ether it is desired to obtain. Thus, for example, we have found that wetting agents are most advantageously prepared by 'sulphonating ethers of the above type in which the fatty alcohol radicals contain from 8 to 14 carbon atoms; more particularly we have found that a sulphonated lauryl ether prepared fromlauryl alcohol in accordance with our invention is a highly effective wetting agent. Suiphonated octyl ethers of our invention are also good wetting agents although these products are not quite as efiective as the'sulphonated Y lauryl ethers. On the other hand, we have found highly eifective wetting properties. Sulphonated ethers derived from" fatty'alcohols containing from 15 to 22 carbon atoins have been found to be eflective detergents. The preferred embodiment of our invention involves the preparation of methaliyl ethers and their sulphonated derivatives, since these compounds may be prepared from-the readily available methallyl alcohol cm (CHF-CEIOH) and since the products obtained from this alcohol have been found to possess cellent properties.

particularly ex.

that the ethers containing fatty alcohol radicals having from 15 to 22 carbon atoms may be most advantageously employed as detergents; for example, suiphonated cetyl" ethers prepared from cetyl alcohol in accordance with our invention have been found to be excellent detergents.

Among the other fatty alcohols which may be employed in accordance with our invention may be mentioned 2-ethyl hexane, 2-01, oleyi alcohol,

7 octadecanol and naphthenyl alcohols. so

The ethers of our invention may be prepared by reacting a sodio derivative of an alcohol having the general formula above given with the chloride of a fatty alcohol containing from 8 to 22 carbon atoms, or, by reacting the chloride of an alcohol of the abcve'formula with the sodio any alcohol having the derivative of the fatty alcohol. In preparing methallyl ethers in accordance with the preferred embodiment of our invention, we prefer to react methallyl chloride with the sodio derivative of the fatty alcohol since methallyl chloride is easily available. The chlorides of either the short chain or fatty alcohols may easily be prepared in a number of ways; preferably they are prepared by reacting the alcohol with an' excess of thionly chloride. In place of the chloride any halide of the alcohol'may be employed. The sodio derivatives of the alcohols may be prepared by reacting these alcohols with sodium or in any other suitable manner.

The ethers of our invention are generally liquids having pleasant odors and yellow to lightbrown colors. They are excellent solvents for fatty materials and may also be used as plasticizers for resins and similar compositions, and as textile lubricants. These ethers may be employed as raw materials for the manufacture of plastics since they tend to polymerize upon heating. They may also be used in conjunction with other substances, 8. g. with solvents or lubricants, in order to impart their desirable properties thereto..

The ethers obtained as above described may sulphonic acid may be employed. It is to be understood that while the products formed by treating the ethers of our invention with sulphonating agents are referred to as sulphonated ethers, the term sulphonated is used in a broad sense and is intended to cover both sulphated-and sulphonated ethers. In view of the varying conditions under which the products of our invention may be prepared and in view of the. different characteristics possessed by these products, we are not certain as to-whether our products are sulphates or sulphonates or a mixture thereof, and hence do not wish to confine our invention'to the production of any particular one of these modifications.

The sulphonated ethers of our invention are capable of a wide variety of uses. As above pointed out, sulphonated ethers having fatty alcohol radicals containing from 8 to 14 carbon atoms are excellent wetting agents, whereas-sulphonated ethers having fatty alcohol radicals containing from 15 to 22 carbon atoms have been found to be effective detergents. We have found that the sulphonated'methallyl ethers of our invention possess wetting or detergent properties far superior to those of the corresponding sulphonated allyl ethers; in some cases we have found that the allyl ethers are extremely dimcult to sulphonate so that surface active agents cannot be obtained therefrom. The sulphonated ethers of our invention may also be employed as foaming agents. softeners and assistants in the cleaning and dyeing of textile material.

The following examples are illustrative of our invention. Amounts are given in parts by weight.

Example I parts of methallyl chloride and 30 parts of the sodio derivative of lauryl alcohol were refluxed for about 12 hours. The reaction mix, ture was then filtered, diluted with water and extracted with ether. The ether extract was separated from the aqueous mass, dried and the ether removed by distillation. The residue was then vacuum distilled and a product boiling at about 146 C. at 17 mm. pressure was recovered. This product upon analysis proved to be methallyl lauryl ether.

20 parts of methallyl lauryl ether were mixed with 10 parts of sulphuric acid and the mixture agitated at a temperature of about 10 C. for 8 'hours. The reaction mass was washed with a 5% sodium chloride solution, neutralized and extracted with ether. separated from the aqueous mass, the ether evaporated therefrom, acetone added to the residue and the acetone partially evaporated. An oily substance separated from the acetone which was extracted with heptane and the extract evaporated to dryness. The residue which remained was sulphonated methallyl lauryl ether.'

Solutions of the sulphonated methallyl lauryl ether were preparedend Draves tests were run thereon to determine the wetting properties of the sulphonated ether. The following, table shows the results of these tests:

The excellent wetting properties displayed by this ether were in striking contrast to the behavior displayed by allyl lauryl ether, since this ether was not readily sulphonated and the sulphonation product did not have any appreciable wetting properties.

Example If 4 parts of sodium were dissolved in 85 parts of methallyl alcohol, 30 parts of cetyl bromide were added thereto and the solution refluxed for 8 hours. The reaction mass was washed with water and the excess methallyl alcohol removed by distillation. The'residue was then vacuum distilled, whereby a fraction boiling, from C. to 159 C. at 2 mm. pressure was obtained; this fraction was found to consist chiefly of methallyl cetyl ether.

20 parts of the methallyl cetyl other were mixed with 10 parts of 100% sulphuric acid and the mixture agitated at temperatures between about 25 C. and about 40 C. The sulphonation mass was then washed with water and neutralized with soda. Sodium chloride and acetone were stirred into the washed mass whereupon three layers separated. The acetone layer was withdrawn, filtered and evaporated to dryness whereby sulphonated methallyl cetyl ether was obtained. This ether displayed excellent detergent properties.

' Example III 3 parts of sodium were dissolved in 34 parts of methallyl alcohol and 24 parts of a mixture of the chlorides of rice bran alcohols, consisting chiefly of oleyl and linoleyl chlorides and prepared by treating the alcohols with thiowl chlo- 75 ride. were added to. the solution. The mixture The ether extract was was then refluxed for 5 hours. The excess methallyl alcohol was removed by distillation and the residue washed, drledand vacuum distilled, whereby the methall'yl others of rice bran oll alcohols were recovered. 25 parts of the ethers were mixed with parts of 100% sulphuric acid, the mixture agitated, washed with salt water and extracted with ether. The ether extract was separated from the aqueous mass and the ether evaporated therefrom, whereby the sulphonated ethers were obtained.

Example IV '11 parts of sodium were dissolved in 255.parts of methallyl alcohol and 47 parts of octyl chloride were added to the solution. The mixture was then refluxed for 6 hours, the excess methallyl alcohol removed by distillation, water added to the mass and the aqueous mass then extracted i was recovered in the usual manner.

It will be evident from the above description that our invention provides new ethers and their sulphonated derivatives, which, because of their highly valuable properties, will be of great interest, particularly to those engaged in the manufacture and treating of textiles and similar mate;

rials.

Since certain changes may be made in the above products and diflerent embodiments of the invention could be made without departing from the scope thereof, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting Having described our invention, what we claim I; A composition of matter comprising essentially an ether having the general formula:

in which R1 and R: denote radicals selected from the group consisting of hydrogen and alkyl radicals containing not. more than 4 carbon atoms; R: denotes an alkyl radical containing not more than 6 carbon atoms; R4 denotes a fatty.

alcohol radical containing from 6 to 22 carbon atoms, and n is a whole number from 1 to 3. l 2. A composition of matter comprising essentially an ether having the general formula:

3 I 3. A composition of matter comprising essentially an ether having the general formula:

I ca e-ciao m in which R4 denotes a fatty alcohol radical containing from 6 to22 carbon atoms.

4. A composition of matter comprising essentially an ether having the general formula:

in which R4 denotes a fatty alcohol radical containing from 8 to 14 carbon atoms.

5. A composition of matter comprising-essentially methallyl lauryl ether.

6. A composition of matter comprising essentially methallyl cetyl ether.

7. A composition of matter comprising essen-- tially methallyl oleyl ether.

8. A composition of matter comprising essentially the sulfonation product of an ether having the general formula:

c=c: cm)..o R4 R. in which R1 and R: denote radicals selected from the group consisting of hydrogen and alkyl radicals containing not more than 4 carbon atoms;

R: denotes analkyl radical containing not more as new and desire to secure by Letters Patent'is:

in which R1 and R: denote radicals selectedfrom the group consisting of hydrogen and alkyl "radicals containing not more than 4carbon atoms; R; denotes-an alkyl radical containing not more than 6 carbon atoms; R4 denotes a fatty alcohol radical containing from 8 to 14 carbon atoms,

and n is a whole number from 1 to 3.

than 6 carbon atoms; R4 denotes a fatty alcohol radical containing from 6 to 22 carbon atoms,

and n is a'whole number from 1 to 3. 9. A composition of matter comprising essentially the sulphonation product of an ether hav- 1 ing the general formula:

in which R1 and R2 denote radicals selected from the group consisting of hydrogen and alkyl radicals containing not more than 4 carbon atoms;

R: denotes an alkyl radical containing not more.

-than 6 carbon atoms; R4 denotes a fatty alcohol radical containing from 8 to 14 carbon atoms, and n is a whole number from 1 to 3.

10. A composition of matter comprising essentially the sulphonation product of an ether having the general formula:

- in which R4 denotes a fatty alcohol radical containing from 6 to 22 carbon atoms.

11. A composition of matter comprising essentially the sulphonation productof an ether hav- -ing the general formula:

in which R4 denotes a fatty alcohol radical containing from 8 to 14 carbon atoms.

12. A composition of matter comprising essentially sulphonated methallyi lauryl ether.

13. A composition of matter comprising essentially sulphonated, methallyl cetyl ether. 14. A composition of matter comprising essentially sulphonated methallyl oleyl ether.

15. A process for the preparation of ethers which comprises reacting a sodio derivative of a fatty alcohol containingfrom 6 to 22 carbon aaaaaai atoms with a compound having the general formula: R1

in which R1 and R2 denote radicals selected from the group consisting of hydrogen and alkyl radicals containing not more than 4 carbon atoms; R3 denotoes an alkyl radical containing not more than 6 carbon atoms; X denotes a halogenatom, and n denotes a whole number from 1 to 3.

16. A process for the preparation of ethers than 6 carbon atoms, and n.is a whole number from 1 to 3.

17. A process for the preparation of ethers which comprises reacting methallyl chloride with a sodio derivative of an alcohol containing from 8 to 14 carbon atoms.

18. A process for the preparation of ethers which. comprises reacting methallyl chloride with the sodio derivative of lauryl alcohol.

19. A process for the preparation oif sulphonated ethers which comprises reacting an ether having the general formula:

in which R1 and R2 denote radicals selected from the group consisting of hydrogen and alkyl radicals containing not more than 4 carbon atoms; R: denotes an alkyl radical containing not more than 6 carbon atoms; R4 denotes a fatty alcohol radical containing from 6 to 22 carbon atoms, and n is a whole number irom 1 to 3 with a sulphonating agent.

20. A process for the preparation of wetting agents which comprises reacting methallyl lauryl ether with a sulphonating agent.

21. A water-soluble salt of the sulphonation product of an ether having the general formula:

CH: cm=d-cmo R. in which R4 denotes a fatty alcohol radical containing from 6 to 22 carbon atoms.

23. A water-soluble salt of sulphonated methallyl lauryl ether.

24. A water-soluble salt of sulphonated methallyl cetyi ether.

25. A water-soluble salt allyl oleyl ether.

DONALD PRICE. BERNARD A. nomaow.

of sulphonated meth- 

